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Local spins: improved Hilbert-space analysis

The decomposition of h <(S) over cap (2)> for a general wave function has been carried out in the framework of the Hilbert-space analysis. The one and two-center components fulfill all physical requirements imposed to date. An inherent ambiguity of the Hilbert-space decomposition of a two-electron quantity, in particular using a Mulliken-type scheme, is also discussed in detail. The formalism of effective atomic densities has allowed us to derive in a simple manner appropriate expressions for the decomposition of <(S) over cap (2)> i in the framework of Hilbert space analysis that are consistent with Mulliken population analysis and related quantities. Using a particular mapping we have derived the Hilbert-space expressions also in the framework of Lowdin population analysis in a straightforward manner. The numerical results obtained with the latter formalism have proved to be more robust and reliable

Financial help has been furnished by the Spanish MICINN Projects No. CTQ2011-23441/BQU, CTQ2011-23156/BQU and Accion Complementaria del MCI (PCI2006-A7-0631). Financial support from MICINN and the FEDER fund (European Fund for Regional Development) was also provided by grant UNGI08-4E-003. E. R.-C. acknowledges support from the Spanish FPU program (Grant No. AP2008-01231). E. M. acknowledges financial support from the EU under a Marie Curie Career Integration grant (PCI09-GA-2011-294240) and the Beatriu de Pinos program from AGAUR for the postdoctoral grant (BP_B_00236). I. M. acknowledges partial financial support from the Hungarian Scientific Research Fund (grant OTKA 71816)

© Physical Chemistry Chemical Physics, 2012, vol. 14, núm. 44, p. 15291-15298

Royal Society of Chemistry

Author: Ramos-Cordoba, Eloy
Matito i Gras, Eduard
Salvador Sedano, Pedro
Mayer, István
Date: 2012
Abstract: The decomposition of h <(S) over cap (2)> for a general wave function has been carried out in the framework of the Hilbert-space analysis. The one and two-center components fulfill all physical requirements imposed to date. An inherent ambiguity of the Hilbert-space decomposition of a two-electron quantity, in particular using a Mulliken-type scheme, is also discussed in detail. The formalism of effective atomic densities has allowed us to derive in a simple manner appropriate expressions for the decomposition of <(S) over cap (2)> i in the framework of Hilbert space analysis that are consistent with Mulliken population analysis and related quantities. Using a particular mapping we have derived the Hilbert-space expressions also in the framework of Lowdin population analysis in a straightforward manner. The numerical results obtained with the latter formalism have proved to be more robust and reliable
Financial help has been furnished by the Spanish MICINN Projects No. CTQ2011-23441/BQU, CTQ2011-23156/BQU and Accion Complementaria del MCI (PCI2006-A7-0631). Financial support from MICINN and the FEDER fund (European Fund for Regional Development) was also provided by grant UNGI08-4E-003. E. R.-C. acknowledges support from the Spanish FPU program (Grant No. AP2008-01231). E. M. acknowledges financial support from the EU under a Marie Curie Career Integration grant (PCI09-GA-2011-294240) and the Beatriu de Pinos program from AGAUR for the postdoctoral grant (BP_B_00236). I. M. acknowledges partial financial support from the Hungarian Scientific Research Fund (grant OTKA 71816)
Format: application/pdf
ISSN: 1463-9076 (versió paper)
1463-9084 (versió electrònica)
Document access: http://hdl.handle.net/10256/8662
Language: eng
Publisher: Royal Society of Chemistry
Collection: MICINN/PN 2012-2014/CTQ2011-23441
MICINN/PN 2012-2014/CTQ2011-23156
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c2cp42513k
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/294240
Is part of: © Physical Chemistry Chemical Physics, 2012, vol. 14, núm. 44, p. 15291-15298
Rights: Tots els drets reservats
Subject: Hilbert, Espais de
Hilbert space
Funcions d’ona
Wave functions
Title: Local spins: improved Hilbert-space analysis
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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